Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/04—Preparations for permanent waving or straightening the hair
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
  • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/44—Preparation of metal salts or ammonium salts
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
  • D06M15/2735—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups of unsaturated carboxylic esters having mercapto groups
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
  • D06M15/3566—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/01—Aerosol hair preparation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S424/00—Drug, bio-affecting and body treating compositions
  • Y10S424/02—Resin hair settings

Definitions

• the present invention pertains to related polymers of medium molecular weight having chains containing thiol functional groups.
• thiols especially a-mercaptocarboxylic acids, such as thioglycolic or thiolactic acid
• a-mercaptocarboxylic acids such as thioglycolic or thiolactic acid
• polysulfhydrylated polymers which are soluble in water, alcohol and organic solvents and comprise sulfhydryl groups in their molecular chains, that is to say polysulfhydrylated polymers, are used instead of low molecular weight thiols, the polydisulfiides formed, either by oxidation due to the action of an outside agent or by oxidation inherent in the process of reacting with the keratin, become insoluble in the solvent. For this reason the action of the polysulfhydrylated polymers on the keratin is accompanied by a supplemental deposit of polymeric material.
• An object of this invention is to produce a new class of polysulfhydrylated polymers.
• Another object of this invention is to produce polysulfhydrylated polymers that are soluble in water and which are particularly desirable for treating keratinic fibers and human hair.
• these polymers may be obtained by starting with previously prepared polymers having in their chains functional reactive groups which are sufiicient to permit 3,484,417 Patented Dec. 16, 1969 'ice a thiol group to be introduced in the usual known manner.
• those polymers particularly suited for use as points of departure for the preparation of polysulfhydrylated polymers to be used according to the invention are the polymers comprising ab initio as a reagent group, the following:
• this group is present in those polymers which are produced by the copolymerization of maleic anhydride with a copolymerizable monomer, that is to say, one having an active double linkage.
• the degree of polymerization n of the different polymers used may vary within wide limits and this is a factor which must be taken into account, depending upon the family of polymers employed.
• the choice of the degree of polymerization It depends on the one hand on the ability of the polymer under consideration to penetrate into the fiber, and on the other hand, on the need for utilizing polymers which are soluble in a selected solvent, such as water, at a basic pH, on the permeability of the fiber to be treated, and the conditions of application (temperature, etc.).
• styrene/maleic anhydride copolymer when a styrene/maleic anhydride copolymer is to be dissolved in an aqueous basic pH solution the degree of polymerization should not be greater than about 20 It is evident that it is impossible to give exact values for all the solvent and polymer combinations envisaged in the present application, but if aqueous solutions are used, it may be said in a general Way that the average molecular weight of the starting polymer used should be less than about 4000.
• the introduction of the thiol group into the said poly mers may be carried out advantageously by reaction with an aminothiol of the formula HSRNHR, in which R designates an alkylene radical comprising preferably from 2 to 4 carbon atoms, which may be substituted by alkyl radicals which may have up to 4 carbon atoms, a carboxyl group or a carbalkoxy group and R represents hydrogen or an alkyl group such as CH C H etc.
• R designates an alkylene radical comprising preferably from 2 to 4 carbon atoms, which may be substituted by alkyl radicals which may have up to 4 carbon atoms, a carboxyl group or a carbalkoxy group
• R represents hydrogen or an alkyl group such as CH C H etc.
• R and R have the meaning disclosed above.
• the polymers thus obtained have a carboxy and a thiol, are soluble in Water in salt form with alkaline metals, ammonia, or amines.
• R and R' are hydrogen, lower alkyl, phenyl or lower alkoxy and n is an integer less than 25 for water soluble polymers and a molecular weight of less than 6000, but n may be higher for other solvents.
• Low molecular weight polymers soluble in basic aqueous solutions are preferred for use on human hair.
• Higher molecular weight polymers, soluble in organic solvents, may be used on fibers, such as wool.
• the polymers are preferably used in compositions having a pH above 4.5.
• EXAMPLE 1 50.5 grams, or 0.25 gram molecules of the unit structure of styrene/maleic anhydride copolymer in which the number n is equal to 8 (a copolymer commercially known as resin SMA 1000 A of the Texas Butadiene Chemical Corp.) is dissolved in 200 cc. of anhydrous acetone.
• This product is started to have styrene monomer/maleic anhydride ratio of 1:199 0.225 gram molecules of ,B-mercaptoethylamine hydrochloride is added to this solution at room temperature under a nitrogen atmosphere.
• 0.225 gram molecules of triethylamine in solution in 50 cc. of acetone is then added slowly, while keeping the temperature between and C. The mixture is then boiled for three hours.
• the triethylamine hydrochloride formed in this manner is drained after cooling and washed with a little acetone.
• the acetonic filtrate is evaporatde until dry under a subatmospheric pressure and a nitrogen atmosphere.
• the residue obtained is purified by dissolving it in a 10% solution of NaOH and reprecipitating it, after drying, by means of a dilute solution of hydrochlorid acid; this yields 60 grams the desired sulfhydryl polymer in the form of a white powder which is then vacuum dried.
• EXAMPLE 2 20.3 g. or 0.1 gram-molecules of the unit structure of maleic anhydride/ styrene copolymer in which the number n is equal to 4 (commercially known as resin SMA 400 A 4 of the Texas Butadiene Chemical Corp.) is dissolved in 200 cc. of anhydrous acetone. A preliminary acidimetric testing of this product indicates that the anhydride group is present in a proportion of only 84%.
• 0.84 gram-molecules of fl-mercaptoethylamine hydrochloride is added to this solution, and while agitating it under a nitrogen atmosphere an acetonic solution of 0.84 gram-molecules of triethylamine is added drop by drop, while keeping the temperature at 1520 C. After this addition, the mixture is brought to reflux for two hours, and the triethylamine hydrochlorate deposited is then dried. The acetonic filtrate is evaporated until dry in a nitrogen atmosphere under sub-atmospheric pressure. The residue obtained is purified by dissolving it in a 10% solution of NaOH and reprecipitating it after drying with a dilute solution of hydrochloric acid. This yields 18 grams of the desired sulfhydrylated polymer in the form of a white powder, which is then vacuum-dried.
• Example 3 20.2 grams, 0.1 gram-molecule of the unit structure of the maleic anhydride/ styrene copolymer, in which the number n is equal to 8 (a copolymer which is commercially known as resin SMA 1000 A of the Texas Butadiene Chemical Corp.) is dissolved in 150 ml. of anhydrous acetone. This product is given as having a styrene monomer/maleic anhydride ratio of 120.9. 0.9 gram-molecules of cysteine hydrochloride are added to this solution at room temperature and under a nitrogen atmosphere. Then 0.9 gram-molecules of triethylamine in solution in 50 cc. of acetone is added slowly, while keeping the temperature between 15 and 20 C. and the mixture is then boiled for three hours. The triethylamine hydrochloride thus obtained is drained after cooling, and washed with a little acetone.
• n a copolymer which is commercially known as resin SMA 1000 A of
• the acetonic filtrate is evaporated until dry under a nitrogen atmosphere at a sub-atmospheric pressure.
• the residue thus obtained is purified by dissolving it in a 10% solution of NaCH and reprecipitating it, after drying, by means of a dilute solution of hydrochloric acid. 24 g. of the desired polymer are thus obtained in the form of a white powder, which is then vacuum dried.
• Example 4 There is used in this preparation the maleic anhydride/styrene copolymer having a molecular weight of about 3000, obtained by copolymerization of styrene with maleic anhydride, in equimolecular proportions, and in the presence of benzoyl peroxide as an activator and normal butyl mercaptan as a regulator, in a conventional manner, by heating to 72 C. for 5 hours.
• Acidimetric analysis of the product indicates that the anhydride group is present in the proportion of 74%.
• an extra purification of the product can be eifected by dissolving it again in an alkaline solution (sodium hydroxide) and reprecipitating it in an aqueous solution of hydrochloric acid. A resilient body is thus obtained which is dried under vacuum. Yield: 75%.
• the properties of resistance to deformation conferred upon fibers by treatment with the solution of polysulfhydryl polymers according to the invention are of value in both the cosmetic field and the textile field, for example, that of wool.
• the polysulfhydrylated polymers are particularly valuable when used for the permanent waving of keratinic fibers. In effect, in this case, fixation by means of oxidizing agents is unnecessary. As indicated above, the poly sulfhydrylated polymers are capable of transformation either at the moment at which they reduce the K4S-K residues of the keratin, or by oxidation in the air, into relatively insoluble reticulated disulfides, and their molecular weight is at least doubled.
• the concentration of the polysulfhydrylated polymers in the compositions for the treatment of keratinic fibers, according to the invention is preferably between 1 and 20%.
• Example 6 A solution having the following composition is prepared:
• EXAMPLE 7 The hair is impregnated with the same solution as the one described in Example 6 and under the same conditions in order to permanently wave it, except that no oxidizing solution is applied. After the period of contact, it is sufficient to copiously rinse the hair for at least two minutes with warm water. This yields a permanent wave which is of good quality and long lasting.
• EXAMPLE 8 The alkaline solution of the polymer described in Example 1 and hereinbefore described also yields excellent results when used for warm permanent waves. For this purpose the operator applies to each curler conventional means used to heat them to a temperature between 65 and C. This produces, after unrolling and without any application of oxidizing lotion, a very pronounced and durable permanent wave.
• EXAMPLE 10 The hair is impregnated with either the solution described in Example 6 or that of Example 9 and a conventional permanent waving process is then carried out. This results in a permanent deformation of the hair which imparts to the resulting wave an appearance and durability substantially superior to those obtained by conventional means. In the course of this waving operation, which comprises the steps of moistening, rolling on curlers, and drying, the excess ammonia evaporates.
• a portion of the polydisulfides which have been formed remain on the fibers, thus imparting to the hair the properties hereinbefore described, by a method which is very easy to carry out.
• R designates an alkylene radical having preferably from 2 to 4 carbon atoms, which may be substituted by lower alkyls having up to 4 carbon atoms, by a carboxyl radical, or by a carbalkoxy group;
• R represents a hydrogen atom or a lower alkyl such as CH or C H I
• R and R" represent a hydrogen atom, a lower alkyl radical, a phenyl radical, or a lower alkoxy radical, with R and R either identical or different
• R represents an -OCOCH radical, a -COOCH radical, or a CN radical
• n is a whole number preferably greater than 1 and less than for water soluble polymers, but higher for polymers soluble in stronger organic solvents.
• An object of this embodiment of the invention is to provide polysulfhydrylated polymers of type II corresponding to the general formula indicated above, in which R and R" both represent a hydrogen atom and in which R represents an OCOCH radical, a -COOCH radical, or a CN radical.
• a further object of this embodiment of the invention is to provide polysulfhydrylated polymers of type II corresponding to the above general formula in which R represents a hydrogen atom, R" represents a -CH radical and R represents the COOCH radical.
• copolymer produced in a conventional manner by copolymerizing in toluene equimolecular quantities of vinyl acetate and maleic anhydride in the presence of benzoyl peroxide, which acts as a catalyst.
• the vinyl acetate/maleic anhydride copolymer used in the present example in a 1% solution in dimethylformamide and at a temperature of 25 C., has a specific viscosity of 0.17.
• the molar ratio between the vinyl acetate and maleic anhydride in this copolymer has been found by measurement of the anhydride function to be 0.93/1.
• the methyl methacrylate/maleic anhydride copolymer used is obtained in a conventional manner by copolymerizing in toluene equi-molecular quantities of methyl methacrylate and maleic anhydride in the presence of diarzo-isobutyronitrile, which acts as a catalyst.
• the molar ratio between the methyl methacrylate and maleic anhydride in this copolymer is determined by measuring the anhydride function to be 1.52/1.
• a yield by weight of a white powder which is soluble in water in an alkaline environment is obtained.
• the process is started with an acrylonitrile/maleic anhydride copolymer obtained in a conventional manner by copolymerizing in toluene equi-molecular quantities of acrylonitrile and maleic anhydride in the presence of benzoyl peroxide, which acts as a catalyst.
• the specific viscosity of this copolymer in a 1% solution in dimethylformamide is 0.055 at a temperature of 25 C.
• the molar ratio between the acrylonitrile and the maleic anhydride in the copolymer is determined, by measurement of the anhydride function, to be 1.19/1.
• the methyacrylate/maleic anhydride copolymer used -as a base is obtained in a conventional manner by polymerizing in toluene equi-molecular quantities of methyl acrylate and maleic anhydride in the presence of benzoyl peroxide, which acts as a catalyzer.
• the ,B-mercaptoethylamine is condensed on the copolymer in the same way as in Example 12 with a yield of 67% by weight of a white powder which is soluble in water at an alkaline pH.
• the base product is the ethylene/maleic anhydride copolymer sold by the Monsanto Chemical Co. under the trademark DX-840l1 resin.
• the specific viscosity of this polymer in a 1% solution in dimethylformamide is 0.1 at 25 C.
• N-methyl-p-mercaptoethylamine hydrochloride 28.6 g. (0.184 mol) of N-methyl-p-mercaptoethylamine hydrochloride and 120 cm. of water are placed in a flask provided with agitating means, a thermometer, and a drop ping funnel.
• the mixture is acidified with concentrated hydrochloric acid, and the precipitate washed with Water and dried.
• the hair is impregnated with this solution and rolled up on curlers in the usual way.
• EXAMPLE 20 A solution having the following composition is prepared for use as a setting lotion:
• the hair is impregnated with this solution and set in a conventional manner.
• This setting operation comprises the following steps:
• a water soluble polysulfhydrylated polymer having keratin reactive SH groups having the recurring formula Cir in which R is selected from the group consisting of alkylene having 2 to 4 carbon atoms, lower alkyl substituted lower alkylene, carboxy-substituted lower alkylene and carbalkoxy substituted lower alkylene, R is selected from the group consisting of hydrogen and lower alkyl, R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl and lower alkoxy, and n is less than 25 and more than 1.
• a water soluble polysulfhydrylated polymer having keratin reactive SH groups having the formula:
• R is selected from the group consisting of alkylene having from 2 to 4 carbon atoms, 1 to 4 carbon atom alkyl substituted alkylene, carboxyl substituted alkylene, and carbalkoxy substituted alkylene;
• R is selected from the group consisting of hydrogen and lower alkyl
• R and R are selected from the group consisting of hydrogen, lower alkyl, phenyl and lower alkoxy;
• R is selected from the group consisting of -OCOCH COOCH and CN, and n is an integer less than 25 and more than 1.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Life Sciences & Earth Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Organic Chemistry (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Engineering & Computer Science (AREA)
• Epidemiology (AREA)
• Birds (AREA)
• Cosmetics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)

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Citations (5)

• 0
  • BE BE629769D patent/BE629769A/xx unknown
  • NL NL290721D patent/NL290721A/xx unknown
• 1963
  • 1963-03-19 GB GB10935/63A patent/GB1002455A/en not_active Expired
  • 1963-03-26 DE DE1444113A patent/DE1444113C3/de not_active Expired
  • 1963-03-28 CH CH398363A patent/CH400087A/fr unknown
• 1967
  • 1967-04-25 US US633394A patent/US3484417A/en not_active Expired - Lifetime
• 1971
  • 1971-02-04 US US00112759A patent/US3741723A/en not_active Expired - Lifetime

Patent Citations (5)

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